Cataltst for synthetic-methanol production



Patented Apr. 25, 1921.

UNITED STATES 4 tezssze PATENT OFFICE.

JOHN C. WOODBUII' AND GROYE B BLOOMEIELD, F TERRE HAUTE, INDIANA, AS-

SIGNORS TO conmmcrar. SOLVENTS CORPORATION, 01 TERRE HAUTE, INDIANA,

A 'QORPOBA'I'ION OI' yABYLAND.

entrants! ron sxnrnnrrc-mnrnanor. rnonocrron.

No Drawing. Original application fled Iay 28, 1926, Serial No. 111,884. Divided and this application 'flled October 14, 1926. Serial No. 141,866. s

oxides of carbon wit hydrogen in the pres-- ence of a suitable catalyst at elevated temperature and pressure. Carbon monoxide, carbon dioxide, and mixtures of the two oxides may be employed, these substances reacting with hydrogen according to the following equations Carbon monoxide-CO 2H;:cH,oH

Carbon dioxide-CO, 3H,T-+ CH,OH H50 It is observed that when carbon dioxide is the oxide employed, one molecule of water is formed :for every molecule of methanol roduced. On the other hand when pure car 11 monoxide is used, theoretically there is nothing produced by the reaction but methanol. Actually in ractice pure carbon monoxide v and pure car on dioxide are both difiicult to obtain economically, so that the methanol synthesis is carried out by reactin a mixture of carbon monoxide and car n dioxide with hydrogen.

:0 In addition to the reactions producing' methanol there are, in the methanol synthesis, undesirable side-reactions which cut down the yield of the desired product The principal side reaction'which ma occur is the formation of methane, whic is illustrated below:

40 In addition to the methane side-reaction there are other side-reactions which sometimes occur in which there are produced esters, aldehydes organic acids,. ketones, and

hydrocarbons 0th merization or condensation of methanol or its decomposition products.

' When a gas, mixture,-comprisinfi carbon oxides mixed with aatxcess of over the amount theoretically required to produce methanol is passed over a catal 'c ,substance com rising metals or their on d es at a pressure a ve 50 atmospheres and at a the consequent destruction of valuable hydr nJgem-is practically eliminated.

er than methane; these re-' actions occurring as the result of the. polytemperature above 250 C. there is nearly always produced some reaction between the gaseous components. The extent of this reaction depends to some degree on space velocity, temperature, and pressure but the fact remains that under the conditions outlined, carbon oxides and hydrogen react to 60 some extent in all cases.

The substances formed by such a process depend both as to identity and as to amount, almost entirely on the nature and activity of the catalytic substance present. The methanol catalysts proposed in the past'have been of two principal types :--i. e.-

1. Mixtures of finely divided metals, or, what is equivalent, mixtures of easily re--. ducible metal oxides;

2. Mixtures of oxides; of metals non-reducible, or diflicultly reducible under the conditions of the methanol synthesis.

In the past, also, one class of easily reducible metal oxides, that is the oxides of iron, nickel, and cobalt have been described as absolutely worthlessfor the production of methanol catalysts since these metals under normal conditions prevent the formation' of methanol, the reaction producing only methane.

We have discovered a new t e'of methanol catalyst which produces a igher 'eld of methanol than those formerly em oycd in the art, and at the same time pro uces a &very puremethanol, uncontaminated by byproducts. An additional advantage accru- 7 mg from the use of our catalysts is that the formation of methane in the process-with e have now discovered a new type of valuable methanol catalyst which comprises three main elements-i. e.

(1) One or more non-reducible metal oxides such as zinc, magnesium, cadmium, chromium, vanadium, tungsten etc.

(2) One or more easil reducible metal ver, I iron, n che],

oxides such-as copper, s1 cobalt, etc.'-;

3) A metallic halide.

t will be observed thatjin. our improved catalyst we ma employ substances normally deleterious tot e methanol react1onnamely the methanating metals -iron,' nickel,- or 10 cobalt. In our improved catalyst composicertain methanol catalysts.

tions these normall deleterious substances Serve advanta eous y, apparently exerting only a norma hydrogenating catalytic action productive of methanol. Or we may employ easily reducible oxides such as those of copper or silver which are already known in the'art as advantageous components of In these cases however, our im roved catalysts containing halides produce ar better results than those known in the art for otherwise identical catalyst mixtures. I

The precise method by which the metallic halides produce the improvement is not known to us. At least three theories may a be used to account for the phenomenonducing duced in the same manner. 3

namely 2-- (1) The metallic halide acts as an ordinar'y promoter in increasing catalyst activity;

(2) The metallic halide interacts with other metallic oxides present in the catalyst to produce oxychloride compounds which, in turn, either serve as catalyst promoters, or may so modify the purely physical state of {he mass as to produce a more active cata- (3) The metallic halide ma be reduced by the high pressure contact wit hydrogen and carbon oxides during the commencement of its use as a catalyst and the resultant finely divided metal may increase the catalyst activity or alternatively, the metallic halide may first react with some other metal prothe halide thereof, which may be re- However, the precise explanation for the improved result attained by the addition of .halide add metallic halides to methanol catalysts is not known and forms no part of our invention.

To produce our improved catalysts it is not necessa that the amount ofmetallic bear any exact weight'relation to the remaining constituents of the cata- 1 st, though the amount of halide added s ould preferably be less than one chemical equivalent of the amount of principal metallic oxide present in the catalyst.

As illustrative of our invention we will cite a specific catalyst containin In order to indicate the efiicacy 0 our catalysts in methanol production we have selected a standard set of conditions of use as follows: The reported yield of condensate from the methanol reaction by use of our catalyst is based on the efi'ect produced when a gas mixture comprising 8% carbon dioxide, 3% of carbon monoxide and 89% hydrogen is passed through 1 liter of catalyst granules at a space velocity of 75,000100,- 000, at a pressure of 2000 pounds, and at a temperature of 340-400 G.

Inselecting a standard set of conditions is it our intention only to thus display the catalyst efiicacy and by no means to limit copper. h

the scope of our invention. Modification of the conditions of the reaction will, of course, modi the results, but the results will always e proportionate to the catalyst empkgyed.

or example, an increased space velocity produces an increased hourly yield and an increase in operatin pressure has the same effect. Likewise e use of pure carbon monoxide as distinguished from carbon dioxide or a mixture of the two results in an increased methanol percentage in the condensate, and, since carbon monoxide seems to react more readily, an increased condensate volume.

. Specific example.

2600 ams of zinc oxide in powdered form is mixe by thorough siftin with 500 grams of black copper oxide. T e resultant mixture is moistened with an aqueous solution containing 150 grams cu rous chloride and 200 grams of dextrin. e resultant mass is dried and broken up into pieces whereupon it is ready for use.

The hourly yield of condensate is about 1.2 liters containing about 40% of methanol.

This application is a division of our 00- pfnding application Serial No. 111,884, filed ay 26th, 1926. In the said ap lication we 95 have claimed, generically, met anol catalysts comprising diflicultly reducible metal oxides, easily reducible metal oxides, and metallic halides and therefore such generic claims are not made herein.

Now having described our invention, we claim the following as new and novel.

1. A methanol catalyst initially comprising a plurality of. difiicultl reducible metal oxides, copper oxide, and a metallic halide.

2. A methanol catalyst initially comprising a difiicultly reducible metal oxide, copper oxide, and a metallic halide.

3. A methanol catalyst initiall compris- 110 mg zinc oxide, chromium oxi e, copper oxide, and ametallic halide. 4. A methanol catalyst initially comprismfiiginc oxide, copper oxide, and a metallic e. 5. A methanol catalyst initially oompris mg zinc oxide, chromium oxide, copper oxide, and cuprous chloride. 6. methanol catalyst intially comprismg zinc oxide, copper oxide, and cuprous chloride. 7. A process for the production of synthet- 1 methanol which comprises pasin a'mixture of hydrogen and carbon oxi es at a pressure 1n excess of atmospheres and 125 at a temperature of 350-450 C. over a catalyst initially comprising a plurality of difiicultly reducible metal oxides, copper oxide, and a metallic halide.

8. A process for the production of synthetio methanol which comprises passing a mixture of hydrogen and carbon oxides at a 10 ture of hydrogen and carbon oxi es at a pressure in excess of 50 atmospheres, and at pressure in excess of 50 atmospheres, and a temperature of 350-450 C. over a catalyst at a temperature of 350-450 C. over acatainitia 1y comprising zinc oxide, copper oxide,

i 1 st initially comprising a difiicultly reducand cuprous chloride. r

i la metal oxide, copper oxide and a metallic In testimony whereof we aflix our signahalide. tures.

' 9. A process for the production of synthet- JOHN G. WOODRUFF. ic methanol which comprises passing a mix- GROVER BLOOMFIELD. 

